Supported catalysts



United States Patent 3,155,627 SUPPQRTED CATALYSTS Edward L. Cole, Glenham, and Edwin" (I. Knowles, Poughlreepsie, N.Y., assignors to Texaco Inc, New York, N.Y., a corporation of Delaware No Drawing. Filed Dec. 29, 196i), Ser. No. 79,112 Claims. (Cl. 252-477) This invention relates to a catalytic structure and, more particularly, is concerned with an improved supported catalyst.

During catalytic processing with solid particulate catalysts, the reactants are passed through a bed of porous catalyst particles, beads or pellets. In many such reactions employing organic materials at elevated temperatures, a carbonaceous deposit accumulates in the pores and openings of the catalyst as the process proceeds under continuous operating conditions. This deposition of carbonaceous material, commonly known as fouling of the catalyst, is a function of the reactants, the reaction products, the conditions of the process, and the catalyst, and certain types of reactions may be worse offenders than others. Fouling may be particularly excessive when the reactants or products remain in contact with the catalyst for a relatively long time. When a porous catalyst is used, the reactants diffuse into the interior or central portion of the catalyst particle and may be retained for an excessive period of time whereupon decomposition of the reactants and products result in fouling of catalyst. Fouling results not only in a decrease in catalyst activity and loss in selectivity, but also results in intensification of the heat transfer problem in the catalyst bed, thereby resulting in local overheating or hot spots, particularly during regeneration of the catalyst. Local overheating and temperature variations in the catalyst bed are deleterious and may result not only in excessive coking of the reactants and inactivation of the catalyst, but also cause undesired side reactions.

This invention has therefore as its purpose to pro vide a catalytic structure devoid of the foregoing disadvantages, and characterized by relatively high activity over long periods of use in any of a wide variety of chemical reactions. The catalytic structure of this invention is provided with an extended substrate having deposited thereon an active catalyst material which affords an effective means for minimizing, or substantially eliminating, local overheating and fouling in the catalyst bed. Equally important, our catalytic structure is not restricted to any particular configuration, and may comprise the Walls of the reactor thereby obviating the need for employing a packed column of catalyst. As a result, the quantity of active catalyst material used in our catalytic structure is greatly reduced as compared to the quantity required in conventional structures. This eliminates a substantial portion of the structural and supporting members of the reactor, permits compactness in design and decreased substantially the capital costs and operating costs. It is significant that the foregoing and other objects are realized without diminishing the flow rates of the reactants, but, on the contrary, in many catalytic processes, the reaction rates may be greatly increased without any appreciable decrease in product yield. These together With other objects and advantages will be apparent to one skilled in the art upon reading the following description.

The novel catalytic structure of our invention involves broadly an extended substrate having deposited thereon a catalyst material, which material may be deposited in a form possessing catalytic activity or capable of being rendered susceptible of catalytic activity by subsequent treatment, as explained more fully hereinbelow. De-

3,155,527 Patented Nov. 3., 1964 "ice pending to a large extent upon the catalyst material employed, our invention was found to be extremely advantageous and economical for use in a number of catalytic processes, conducted either in liquid or vapor phase.

The extended substrate, as employed herein, and in the appended claims, is defined as a substrate of extended dimensions and is particularly of a length and geometric surface area substantially greater than that of discrete particles. The extended substrate is not less than about inch in its maximum dimension, and more preferably /4-inch and of sufiicient thickness to provide the required physical strength.

The catalytic structure is formed in accordance with our invention by chemically reducing a solution containing a soluble compound of the catalyst material in the presence of an extended substrate under such conditions as to effect a substantially uniform deposition of the catalyst material upon the substrate. Although the exact form of the deposits cannot be determined, it is believed that the material is deposited as elemental metal or its intermediate product of reduction, such as the oxide. Chemical reduction of the deposit is particularly applicable to those metals Whose salts or compounds in solution form a soluble complex with a suitable stabilizing agent such as complexing agents which form soluble complex ions of the coordinate complex type, sequestering agents, chelating agents, dispersants and detergents. Salts of numerous metals form with ammonia, for example, a soluble complex ion. The metal complex may be readily reduced to the elemental form, or its intermediate product of reduction, with a suitable reducing agent, hereafter described in greater detail. Metals from Groups I, VI and VIII of the Periodic Table of Elements, for example, copper, silver, gold, chronium, tungsten, molybdenum, iron, nickel, osmium, platinum and palladiurn are generally suitable for use in the present process. Other elemental metals, including many from Groups 11, Ill, IV, V and VII of the Periodic Table, for example, zinic, aluminum, tin, zirconium, titanium, vandiurn, tantalum and manganese, can also be used.

The non-metallic ion or anion of the metal compound or salt to be precipitated from the ammoniacal solution may be of the more common inorganic or organic acids which form soluble salts of the metal. Also, the anion should not be reduced under precipitation conditions. Those anions usually employed include sulfate, chloride, nitrate, carbonate and acetate. The solvent generally used is water to form an aqueous solution of the metal complex, but suitable organic solvents for the metal salts, including alcohols, aldehydes, ethers, ketones, toluene and pyridine may be useful as may be liquid ammonia.

Although ammonia is the preferred stabilizing agent and the invention is described in greater detail in connection with solutions of this type, certain other stabilizing agents may be employed. Other suitable stabilizing agents include the organic primary, secondary and tertiary amines, such as methyl amine, ethylenediamine and diethylenetriamine. In addition, complexing agents may include phosphates, especially pyrophosphate and metaphosphate, as well as citrate, acetate, oxalate, tartrate, ophenanthrolene, thiocyanate, thiosulfate, thiourea, pyridine, quinoline and cyano groups. Still further useful complex formations include the chloro, hydroxo and aquo complexes, such as the aquo-ammonia complexes. Olefin and olefin-like compounds are also useful and may include, for example, ethylene, propylene, butadiene, etc., as well as the unsaturated cyclo compounds, such as cyclohexene and styrene. However, the olefin and olefin-like compounds are desirably employed in a non-aqueoussolvain, for example, benzene, toluene, pyridine, acetone and e er.

The concentration of the particular metal in solution will depend to a considerable extent upon the metal employed. Generally, there appears to be no benefit from employing concentrations in excess of about 5 mols, but the concentration of a metal in solution should be less than that at which a substantial amount will precipitate out in particulate form which may be determined by experiment by one skilled in the art. A concentration of less than about 0.01 mol is usually too low for effecting reduction within a reasonable period of time. We have found a concentration of 0.5 to 2 mols to be generally satisfactory, but with the more rare or expensive elements, such as platinum, the concentration may advantageously be as low as 0.04 mol.

The elemental metal, or its intermediate product of reduction, is plated onto the extended substrate from the solution of the dissolved metal salt by treating the solution with a reducing agent, preferably a reducing gas, in the presence of the substrate. In the preferred embodiment of our invention, the substrate is immersed or otherwise contacted with the solution containing a soluble compound of the catalyst material, and the solution pressured with hydrogen at an effective reduction temperature, often at elevated temperatures and under superatmospheric pressures. The temperature and pressure employed in the reducing step depend to some extent upon the material undergoing reduction and may vary over a wide range. Thus, for example, platinum may be deposited from ethylene chloroplatinate in benzene by reduction with hydrogen at room temperature and atmospheric pressure. However, with numerous other metals, reduction proceeds advantageously at elevated temperatures which may range up to about 500 F., and under a partial pressure of reducing gas of as high at 4,000 pounds per square inch or higher. Although higher temperatures and pressures may increase slightly the rate of the reduction reaction, this increase generally is not significant.

It should be understood that other reducing gases, such as carbon monoxide, may be used with satisfactory results, as may other reducing agents, for example, hydrazine, hydroxylamine, glyoxal, formaldehyde, or sulfur dioxide.

The extended substrate employed in a catalytic structure formed in accordance with our invention is not restricted to any particular configuration nor to any particular material. The substrate may be formed of a metal or a nonmetal suitable for use in a catalytic reactor and may include such materials as aluminum, steel, stainless steel, nickel or titanium, including sintered metal materials, or refractory materials including, for example, refractory metal oxides, e.g., alumina, magnesia, silica, or refractory metal silicates or carbides. The configuration of the extended substrate may include bars, balls, chain, mesh, plates, saddles, sheet, tubes, wire or the like.

By Way of example, elemental platinum, useful as a reforming catalyst, may be deposited on the substrate from an ammoniacal solution of a platinum salt, e.g., the chloride salt or chloroplatinic acid, by reducing the solution with hydrogen at elevated temperature and pressure as described above. Similarly, a silver deposit useful as a catalyst in the oxidation of ethylene may be formed on the substrate from an ammoniacal solution of silver sulfate. On the other hand, a deposit of nickel or of molybdenum similarly formed may be sulfided with hydrogen sulfde gas at elevated temperature, and the resulting sulfide catalyst then used in hydrogenation processes. A deposit of chromium or a deposit of iron may be oxidized for use as a catalyst in polymerization of olefins and the reaction of carbon monoxide with hydrogen to produce hydrocarbons, respectively.

A mixture of metal salts, all of which form complex ions with ammonia or other suitable stabilizing agents may be used for forming a deposit of more than one catalytic element. By such means, a nickel-molybdenum catalyst or cobalt-molybdenum-nickel catalyst may be deposited on the substrate for use as hydrogenation catalysts. Also, nickel-molybdenum or nickel-tungsten salts may be complexed in a sodium citrate solution, and the metals precipitated from solution with hydrogen as described above. The co-deposits may then be calcined, sulfided, or oherwise activated when desired.

It will be observed that the choice of added catalyst material depends upon the use contemplated. Thus, the catalytic structure of our invention may be advantageously employed in a wide variety of catalytic processes including such typical operations as isomerization, polymerization or alkylation of paraffinic and aromatic hydrocarbons. In addition, the catalytic structure may be useful in the hydration and hydrogenation of olefins, or in the dehydrogenation or oxidation of various organic compounds such as in producing an aldehyde or ketone from the corresponding alcohol, as well as in various cracking reactions and halogenation-dehalogenation processes.

In order to assure deposition of the desired quantity of the catalyst material, it may be necessary in some cases to repeat the particular process employed in depositing the material including the successive steps of deposition, and drying or activation where required. Depending on the added catalyst deposit and its intended use, the substrate may be substantially inert catalytically, or it may have a synergistic effect upon the catalyst material. It should be understood that a suitable promoter or inhibitor may be added to the catalyst material, or incorporated with the reactants undergoing catalytic treatment.

It will be observed that the deposited film of metal as catalyst material formed on an extended substrate in ac-- cordance with our invention defines the depth of the catalyst layer and therefore limits the extent of diffusion of the reactants through the pores or openings in the catalyst material to this shallow depth. As a consequenw, substantially all of the active catalyst is exposed to the reactants, and excessive residence time, or entrapment, of the reactants is minimized or substantially eliminated. In this manner, we readily achieve with less catalyst material a reactive capacity equal to, or greater than, that accomplished by conventional catalysts.

In a preferred embodiment of our invention, the catalytic structure is provided in the form of a metal tube of relatively small inside diameter. The inside diameter of the tube, in general, may range from about 0.05 to 0.5 inch, but is dependent upon the type of catalytic reaction and the material undergoing reaction. The added catalyst material is deposited on at least one wall surface of the tube, and advantageously on the interior wall of the tube. The tube through which the reactants pass is preferably of a continuous length sutlicient to accomplish the desired catalytic reaction in economic yields, but may be coiled to conserve space. The length of the tube may depend to some extent upon the reaction contemplated, and therefore may be readily determined by one skilled in the art. The wall of the reactor provides adequate support and mechanical strength for the catalyst, and thereby affords a substantially self-sustaining structure. Packed reaction columns are eliminated as are many of the structural and supporting features employed in a conventional catalytic reactor.

It will be observed that the metal tube provides an adequate means to control the temperature of heat transfer to or from the catalyst. The metal wall, being a good heat conductor, may be employed as a heat exchanger. A suitable heat exchange medium may be applied to the exterior Wall of the metal tube. During processing, the heat evolved in the catalyst bed is readily conducted by the Wall of the tube to the surroundings Where it is absorbed and dissipated by the heat exchange medium. On the other hand, the tubular wall may be employed for supplying heat from a heating medium in the case of an endothermic reaction. This invention also contemplates that the catalyst material may be deposited on the exterior wall surface of the tube, and the heat exchange medium passed through the interior thereof. It should be understood that in an economic and commercial operation, a number of the catalytic tubes may be housed in a single unit in parallel and arranged in contacting relation with a heat exchange medium.

It is of further significance that in the catalytic tube having a relatively small inside diameter, highly turbulent flow of the reactants passing through the tube is readily maintained. As a consequence, near maximum reaction rates are achieved. In addition, the catalytic structure of our invention markedly reduces the residence time of the reactants in the reactor, as explained above. Consequently, the reactor may be operated at high temperatures, or optimum temperatures, or, more important, in many cases at higher temperatures and faster rates than those normally encountered in a conventional reactor, without danger of excessive coking or fouling of the catalyst.

The catalytic tube or sheet formed in accordance with the invention is of further advantage in that the reactant gases in certain processes may be caused to pass through the tube or sheet by use of a pervious or permeable tube or sheet, optionally with the application of a pressure differential between the interior and exterior of the tube or opposite sides of the sheet. A porous tube or wall may be formed from powdered metal, preferably sintered, by known procedures in the field of powder metallurgy. Thus, for example, in a hydrogenation process, hydrogen may be diffused through the tube and into immediate contact with the catalyst surface where reaction occurs, thereby more fully utilizing the reactants and increasing the reaction rates. In other processes, the reactant gases may be caused to pass in or out of the catalyst tube through the permeable wall of the tube.

The following examples will further illustrate our invention.

EXAMPLE I A coil of stainless steel tubing measuring 20-feet in length and having an inside diameter of -inch and an outside diameter of /s-inch was initially cleaned by etching in an aqueous 15% hydrochloric acid solution. The interior wall surface of the tube was impregnated with molybdenum oxide catalyst as follows:

A solution of the catalyst was prepared by adding to 250 milliliters of water, 62 grams of ammonium molybdate tetrahydrate and 33 grams of ammonium sulfate. 30 grams of ammonium hydroxide (28.7% by weight HN OH) was added and the solution heated to boiling. The volume of the solution was reduced to 250 milliliters by evaporation.

The stainless steel tube was filled with the above prepared catalyst solution and placed in an autoclave, the.

ends of the tube remaining open. The autoclave was flushed with hydrogen and then pressurized with hydrogen at 3,000 p.s.i.g. at 300 F. and 5 hours. The autoclave was then depressurized and cooled to room temperature. The stainless steel tube was removed from the autoclave, dried at 160 F. and then calcined at 750 F. for 2 hours in air. The net gain in weight of the tube was 2 grams.

The treated tube bearing the molybdenum oxide catalyst deposit on its interior wall surface was employed as a reactor in the oxidation of methanol to formaldehyde. Air, at about 60 F., was used to evaporate the methanol charged to the reactor. The conditions for the reaction,

and the results obtained are set forth in Table I, below:

Table I Pressure Atmospheric Reactor temperature, F.

Contact time, seconds 10.36 Air, Cubic ft./hr. 1.7 Methanol charged, grams total 18 Formaldehyde recovered, grams total 6.3

Grams formaldehyde/ grams MoOx/hr. 0.79 Conversion of formmdehyde, weight percent 35 1 6 The formaldehyde was recovered in a water washed tower. Selectivity for the reaction was greater than The by-products included methyl alcohol, dimethyl ether and hydrogen.

' EXAMPLE II Nickel chips measuring approximately A by A by V were impregnated with a cobalt-molybdenum-nickel catalyst as follows: A solution of the catalyst material was prepared by adding 1,500 milliliters of water, 112 grams of nickel sulfate hexahydrate, 73 grams of cobalt sulfate heptahydrate, 89 grams of ammonium molybdate tetrahydrate and grams of ammonium sulfate. The mixture was heated at 180 F., and 500 milliliters of ammonium hydroxide (28.7% by weight NI-I OH) was added with stirring to dissolve all the salts.

146.83 grams of nickel chips were placed in a glass tube and covered with 200 milliliters of the above catalyst solution. The tube was placed in an autoclave, flushed with hydrogen, and then pressurized with hydrogen at 1,100 p.s.i.g, at 350 F. and for 5 hours. The autoclave was depressurized, cooled to room temperature, and the treated nickel chips removed. The nickel chips were dried at F. for 2 hours, and then calcined at 750 F. for 2 hours in air. The net gain in weight of the nickel chips was 12.44 grams.

The prepared nickel chips, having the catalyst imbedded thereon, were used as a catalyst in a fixed bed reactor for a hydrogenation process. A wax distillate fraction obtained upon distillation of a Mid-Continent paraffinic crude which had been furfural refined to remove a substantial portion of aromatics was employed as the charge stock. Table II, below, shows the conditions for the process.

Table II Pressure, p.s.i.g 1125 Reactor temperature, F. 575 Liquid space velocity, v./v./hr. 0.81

Recycle rate of gas (from high pressure separator) s.c.f./bbl.

The color of the charge stock was reduced from 225, as measured on a Lovibond colorimeter employing a 6- inch cell, to 25 Lovibond 6-inch cell in the final product. In addition, the sulfur content in the charge stock was reduced from 0.42% by weight to 0.15% in the product.

EXAMPLE III Table III Pressure, p.s.i.g 1000 Reactor temperature, F. 654 Liquid space velocity, v./v./hr. 1.55 Recycle rate of gas, s.c.f./bbl. 5000 The charge stock had a color of 75 Lovibond /2-inch cell, while the color of the final product measured 60 Lovibond 6-inch cell.

EXAMPLE IV Alumina pellets, measuring aproximately /s-inch in diameter, the total weight of the pellets being 119 grams, were impregnated with the catalyst material of Example II and by substantially the same method as that employed in Example II. The impregnated pellets were calcined for 5 hours at 750 F. in air. The net gain in weight was 9 grams. A wax distillate fraction similar to that used in Example 11 was hydrogenated, the conditions for which are shown in Table IV, below.

Recycle rate of gas, s.c.f./bbl. 10,000

The color was improved from 55 Lovibond /2-inch cell to 10 Lovibond 6-inch cell.

We claim:

1. A catalytic structure consisting essentially of a support and a metal catalyst material deposited on said support by immersing said support in a solution containing a soluble compound of said catalyst material, pressuring said solution with hydrogen and maintaining said solution at an effective reduction temperature thereby depositing a substantially uniform film of said catalyst material on said support.

2. A catalytic structure consisting essentially of an extended metal tubular substrate of relatively small diameter as conduit for reactants undergoing catalysis, and an added metal catalyst material deposited on the inner wall surface of said tubular substrate by chemical reduction from a solution containing a soluble compound of said catalyst material by pressuring said solution with hydrogen in the presence of said substrate.

3. A catalytic structure consisting essentially of an extended metal tubular substrate of relatively small diameter for passage therethrough of reactants undergoing catalysis, and an added catalyst material deposited on the interior wall surface of said tubular substrate by contacting said interior wall surface of said tubular substrate with an aqueous ammoniacal solution of a compound of said catalyst material, pressuring said solution with hydrogen and maintaining said solution at an effective reduction temperature thereby depositing a substantially uniform film of said catalyst material on said interior wall surface.

4. A method for preparing a catalytic structure which comprises contacting a support with a solution of a soluble compound of metal catalyst material; and subjecting said solution to chemical reduction by pressuring said solution with hydrogen whereby a catalyst material is deposited on said support.

5. A method according to claim 4 wherein said chemical reduction is effected by pressuring said solution with hydrogen while maintaining said solution at an elevated temperature.

6. A method according to claim 4 wherein said support comprises an extended metal tubular substrate of relatively small diameter.

7. A method for preparing a catalytic structure comprising metal-containing materials as co-deposits of more than one metal on a support which comprises contacting said support with an aqueous ammoniacal solution of soluble complexes of the metals to be co-deposited on said support, the concentration of each of said metals in solution being not less than 0.01 molar, pressuring said solution with hydrogen while maintaining said solution at an elevated temperature whereby said metal-containing materials are co-deposited onto said support and subsequently activating said co-deposits for use as a catalyst material.

8. A catalytic structure according to claim 1 wherein said support comprises metal wire.

9. A catalytic structure according to claim 1 wherein said support comprises metal mesh.

10. A method according to claim 4 wherein said solution is an aqueous ammoniacal solution.

References Cited in the file of this patent UNITED STATES PATENTS 2,339,929 Houghton Jan. 25, 1944 2,515,279 Van der Hoeven July 18, 1950 2,611,736 Haensel Sept. 23, 1952 2,644,800 Mottern et al July 7, 1953 2,760,940 Schwarzenbek Aug. 28, 1956 2,778,610 Bruegger Jan. 22, 1957 2,852,564 Warner et a1. Sept. 16, 1958 2,906,700 Stine Sept. 29, 1959 2,974,150 McClements et al Mar. 7, 1961 3,055,842 Robinson Sept. 25, 1962 

1. A CATALYTIC STRUCTURE CONSISTING ESSENTIALLY OF A SUPPORT AND A METAL CATALYST MATERIAL DEPOSITED ON SAID SUPPORT BY IMMERSING SAID SUPPORT IN A SOLUTION CONTAINING A SOLUBLE COMPOUND OF SAID CATALYST MATERIAL, PRESSURING SAID SOLUTION WITH HYDROGEN AND MAINTAINING SAID SOLUTION AT AN EFFECTIVE REDUCTION TEMPERATURE THEREBY DEPOSITING A SUBSTANTIALLY UNIFORM FILM OF SAID CATALYST MATERIAL ON SAID SUPPORT. 